WO2000055108A1 - VERFAHREN ZUR HERSTELLUNG CYCLISCHER α, β-UNGESÄTTIGTER KETONE - Google Patents

VERFAHREN ZUR HERSTELLUNG CYCLISCHER α, β-UNGESÄTTIGTER KETONE Download PDF

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Publication number
WO2000055108A1
WO2000055108A1 PCT/EP2000/001640 EP0001640W WO0055108A1 WO 2000055108 A1 WO2000055108 A1 WO 2000055108A1 EP 0001640 W EP0001640 W EP 0001640W WO 0055108 A1 WO0055108 A1 WO 0055108A1
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WO
WIPO (PCT)
Prior art keywords
reaction
oxygen
catalysts
mol
formula
Prior art date
Application number
PCT/EP2000/001640
Other languages
German (de)
English (en)
French (fr)
Inventor
Rolf Fischer
Rolf Pinkos
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP00909260A priority Critical patent/EP1161409B1/de
Priority to US09/914,796 priority patent/US6433229B1/en
Priority to DE50003184T priority patent/DE50003184D1/de
Priority to JP2000605539A priority patent/JP2002539180A/ja
Publication of WO2000055108A1 publication Critical patent/WO2000055108A1/de

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for the preparation of cyclic, ⁇ , ⁇ -unsaturated ketones by dehydrogenating cyclic ketones at elevated temperature in the absence of oxygen or less than 0.5 mol of oxygen per mol of starting ketone in the presence of catalysts which have a BE surface of at least 0.5 m 2 / g.
  • cyclic ⁇ , ⁇ -unsaturated ketones from the corresponding saturated ketones in the gas phase is e.g. for the case cyclopentenone by F. Delies, J. Am. Chem. Soc. 91, 27 (1969) by uncatalyzed gas phase pyrolysis at 532 to 581 ° C in a vacuum.
  • the cyclopenenone yields and selectivities that can be achieved are very low, since decomposition predominates.
  • This object was achieved according to the invention with a process for the preparation, in particular the continuous production of cyclic, ⁇ , ⁇ -unsaturated ketones of the formula II by dehydrogenation of cyclic ketones of the formula I. o 0
  • n is one of the numbers 1 to 10 and which may optionally be substituted, at elevated temperature in the presence of catalysts in the gas phase, the reaction being carried out in the absence of oxygen or in the absence of less than 0.5 mol of oxygen / mol of the Compound I at temperatures of 250 to 600 ° C and with catalysts with a BET surface area greater than 0.5 m 2 / g.
  • the cyclic enones or ketones of the formulas II and I can also carry substituents on the ring C atoms.
  • substituents are e.g. Alkyl or aryl radicals.
  • Preferred starting ketones are cyclohexanone and especially cyclopentanone.
  • the reaction is preferably carried out in the absence of oxygen, but the reaction can also be carried out with certain amounts of oxygen, e.g. be carried out with up to 0.2 mol of oxygen per mol of ketone.
  • the reaction temperatures of the process according to the invention are generally between 250 and 600 ° C, preferably 300 to 575 ° C and in particular 350 to 550 ° C.
  • the reaction pressure is generally between 0.1 and 10 bar, preferably 0.5 to 6 bar and in particular 0.9 to 3 bar.
  • the cyclic ketones can be reacted with or without a carrier gas. If you work with carrier gas, inert gases such as e.g. Methane, nitrogen or argon are used.
  • Air or mixtures of air with inert gas or with pure oxygen or mixtures of oxygen with inert gases are metered.
  • the molar ratio of oxygen to ketone should generally not exceed 0.1.
  • the molar ratio is preferably less than 0.01, particularly preferably in the absence of oxygen.
  • the process according to the invention can be carried out in the presence of water.
  • the amount of water is generally not critical, but is preferably between 0.01 and 1 kg, particularly preferably between 0.05 and 0.2 kg of water per kg of cyclic Ketone.
  • the addition of water generally extends the life of the catalyst.
  • the BET surface area of the catalysts to be used according to the invention is generally 0.5 to 2000, preferably 1 to 500 and in particular 2 to 200 m 2 / g.
  • Oxidic materials are particularly suitable as catalyst masses. These are above all catalysts which contain oxides of the elements of groups 2 to 14 of the periodic table of the elements or consist of these.
  • Examples include magnesium oxide, titanium dioxide, zirconium dioxide, chromium III oxide, cobalt oxide, copper oxide, zinc oxide, aluminum oxide and silicon dioxide.
  • the oxides can be uniform or mixed. Different oxides can form homogeneous mixed oxides by co-precipitation or can be in a mechanical mixture.
  • Activated carbon or silicon nitride can also be mentioned as catalytically active base materials with a large surface area.
  • the aforementioned large surface area catalytic materials can also e.g. in amounts of 0.01 to 5% by weight, contain compounds from elements of the 1st, 15th and 16th group of the Periodic Table of the Elements. These elements are e.g. Na, K, P or S, usually in the form of the oxides.
  • metallic components preferably also in the form of the oxides, of the 7th to 11th groups of the periodic table of the elements can be applied, especially to the oxidic base materials mentioned.
  • metallic components include rhenium, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper and silver.
  • the following catalysts are particularly suitable: CuO, AgO, PdO, NiO, Mn 2 0 3 or Re 2 0 7 on ZnO, CaO, BaO, Si0 2 or A1 2 0 3 .
  • These catalysts are prepared in a manner known per se, for example by soaking and calcining or by precipitating hydroxides or carbonates and calcining, as described, for example, in Charles N. Satterfield, Heterogeneous Catalysis in Industrial Practice, 2nd edition, New York Mc Graw -Hill, is described.
  • the process according to the invention can be carried out over permanently arranged or moving catalysts.
  • suitable types of reactors are fixed bed reactors, fluidized bed reactors and riser reactors.
  • the inorganic-based catalyst can generally be completely regenerated by burning off the deposits, e.g. at 400 to 500 ° C with air.
  • reaction can be carried out in a single pass, the resulting product mixture then being worked up and any unreacted starting material being recycled, or the reaction product can be returned to the reactor before working up in order to increase the conversion.
  • Cyclic enones such as Cyclopentenone or cyclohexenone are sought-after intermediates for the production of active pharmaceutical ingredients or crop protection agents.
  • Example 1 The procedure described in Example 1 was carried out using the further catalysts indicated in Table 1, and the results given there were obtained.
  • Example 5 4 NL / h of air were metered in in addition to 20 NL / h of nitrogen.
  • the Cu rings used in Example 5 were treated with oxygen at 500 ° C. before the reaction.
  • Example 7 cyclopentanone was used, which contained 5% water.
  • Example 2 Analogously to Example 1, 100 ml of ZnO cyclopentanone were reacted at 500.degree. After a running time of about 48 hours and a feed amount of about 1 liter, 85.1% by weight of cyclopentanone and 14.5% by weight of cyclopentenone were found in the discharge. The discharges collected were distilled at 1013 mbar on a 40 cm packed column. Cyclopentenone with a purity of approximately 99.6% was obtained.
  • cyclopentanone was reacted on ZnO at 400 ° C. After a running-in phase of 0.5 h, the reaction product was collected over a period of about 20 h. It had the following composition: cyclopentanone 95.1% by weight, cyclopentenone 4.2% by weight. This product mixture was then used again. 92.5% by weight of cyclopentanone and 6.6% by weight of cyclopentenone were found in the reaction discharge.
  • Example 2 According to the information in Example 2 (CuO / ZnO; BET surface area 15 m 2 / g), cycloheptanone was reacted at 400.degree. 95% by weight of unreacted starting material, 1% by weight of cycloheptenone and 1.3% by weight of cresol as well as other quantities of insignificant quantity were found in the discharge.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
PCT/EP2000/001640 1999-03-12 2000-02-28 VERFAHREN ZUR HERSTELLUNG CYCLISCHER α, β-UNGESÄTTIGTER KETONE WO2000055108A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP00909260A EP1161409B1 (de) 1999-03-12 2000-02-28 Verfahren zur herstellung cyclischer alpha, beta-ungesättigter ketone
US09/914,796 US6433229B1 (en) 1999-03-12 2000-02-28 Method of producing cyclic, α, β-unsaturated ketones
DE50003184T DE50003184D1 (de) 1999-03-12 2000-02-28 Verfahren zur herstellung cyclischer alpha, beta-ungesättigter ketone
JP2000605539A JP2002539180A (ja) 1999-03-12 2000-02-28 環状α，β−不飽和ケトンの製法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19911169.3 1999-03-12
DE19911169A DE19911169A1 (de) 1999-03-12 1999-03-12 Verfahren zur Herstellung cyclischer alpha, beta-ungesättigter Ketone

Publications (1)

Publication Number Publication Date
WO2000055108A1 true WO2000055108A1 (de) 2000-09-21

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PCT/EP2000/001640 WO2000055108A1 (de) 1999-03-12 2000-02-28 VERFAHREN ZUR HERSTELLUNG CYCLISCHER α, β-UNGESÄTTIGTER KETONE

Country Status (7)

Country Link
US (1) US6433229B1 (ja)
EP (1) EP1161409B1 (ja)
JP (1) JP2002539180A (ja)
CN (1) CN1170803C (ja)
DE (2) DE19911169A1 (ja)
ES (1) ES2204527T3 (ja)
WO (1) WO2000055108A1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005009937A1 (de) * 2003-07-24 2005-02-03 Basf Aktiengesellschaft Verfahren zur dehydrierung von carbonylverbindungen

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073157A2 (de) * 2004-01-30 2005-08-11 Basf Aktiengesellschaft Katalytisch aktive zusammensetzung und ihre verwendung in dehydrierverfahren
DE102004011543A1 (de) 2004-03-08 2005-10-06 Basf Ag Verfahren zur Herstellung optisch aktiver Carbonylverbindungen
CN102442895B (zh) * 2011-12-22 2015-04-08 江苏扬农化工集团有限公司 一种用环己烯合成环己烯酮的方法
US10899694B2 (en) 2016-06-27 2021-01-26 Firmenich Sa Dehydrogenation reaction
CN107952459B (zh) * 2017-12-07 2020-08-28 万华化学集团股份有限公司 大环烯酮的合成方法、及一种催化剂和它的应用
CN110790649A (zh) * 2019-11-07 2020-02-14 西北大学 一种合成多取代α,β不饱和酮的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3364264A (en) * 1965-01-25 1968-01-16 Standard Oil Co Process for the manufacture of olefinically unsaturated ketones

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3476808A (en) * 1967-05-17 1969-11-04 Mobil Oil Corp Catalytic oxidative dehydrogenation of ketones

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3364264A (en) * 1965-01-25 1968-01-16 Standard Oil Co Process for the manufacture of olefinically unsaturated ketones

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005009937A1 (de) * 2003-07-24 2005-02-03 Basf Aktiengesellschaft Verfahren zur dehydrierung von carbonylverbindungen
US7285685B2 (en) 2003-07-24 2007-10-23 Basf Aktiengesellschaft Method for dehydrogenation of carbonyl compounds
CN100427445C (zh) * 2003-07-24 2008-10-22 巴斯福股份公司 羰基化合物的脱氢方法

Also Published As

Publication number Publication date
DE19911169A1 (de) 2000-09-14
EP1161409A1 (de) 2001-12-12
US6433229B1 (en) 2002-08-13
CN1170803C (zh) 2004-10-13
ES2204527T3 (es) 2004-05-01
JP2002539180A (ja) 2002-11-19
CN1343191A (zh) 2002-04-03
DE50003184D1 (de) 2003-09-11
EP1161409B1 (de) 2003-08-06

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